Hydrotreating catalyst with a titanium containing carrier and sulfur containing organic additive

Abstract

Generally, it is disclosed a catalyst for use in a hydrotreating hydrocarbon feedstocks and the method of making such catalyst. It is generically provided that the catalyst comprises at least one Group VIB metal component, at least one Group VIII metal component, about (1) to (about (30) wt % C, and preferably about (1) to about (20) wt % C, and more preferably about (5) to about 15 wt % C of one or more sulfur containing organic additive and a titanium-containing carrier component, wherein the amount of the titanium component is in the range of about (3) to (about (60) wt %, expressed as an oxide (Ti0 2 ) and based on the total weight of the catalyst. The titanium-containing carrier is formed by co-extruding or precipitating a titanium source with a Al203 precursor to form a porous support material comprising Al 2 0 3 or by impregnating a titanium source onto a porous support material comprising Al 2 0 3 .

The invention claimed is: 
     
       1. A method of producing a catalyst, the method comprising
 co-extruding a titanium source with a porous material comprising Al 2 O 3  to form a titanium-containing carrier extrudate, 
 drying and calcining the extrudate, and 
 impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, 
 
       the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst. 
     
     
       2. A method of producing a catalyst, the method comprising
 precipitating a titanium source with an aluminum source, 
 extruding the precipitate to form a titanium-containing carrier extrudate, 
 drying and calcining the extrudate, and 
 impregnating the calcined extrudate with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, 
 
       the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst. 
     
     
       3. The method of  claim 2  wherein the precipitation comprises the steps of (a) simultaneous dosing of sodium aluminate and aluminum sulfate to water at a fixed pH (b) the formed alumina filter cake is re-slurried in water (c) to this slurry TiOSO 4  or titanium sulfate is added at a fixed pH>7 controlled by an alkaline solution. 
     
     
       4. The method of  claim 2  wherein the precipitation comprises the steps of (a) the aluminum source and the titanium source are mixed in one stream and sodium aluminate is dosed either simultaneously or subsequently to water at a pH>7. 
     
     
       5. A method of producing a catalyst, the method comprising
 impregnating a porous material comprising Al 2 O 3  with a titanium source to form a titanium-containing carrier, 
 drying and calcining the carrier, and 
 impregnating the calcined carrier with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source, 
 
       the amount of the titanium source being sufficient so as to form a catalyst composition at least having a titanium content in the range of about 1 wt % to about 60 wt %, expressed as an oxide (TiO 2 ), based on the total weight of the catalyst. 
     
     
       6. The method of  claim 1 ,  2  or  5  further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in a single step with a solution comprising a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source. 
     
     
       7. The method of  claim 1 ,  2  or  5  further comprising the impregnation with a sulfur containing organic additive, at least one Group VIB metal source and/or at least one Group VIII metal source being performed in more than one step, wherein the carrier is impregnated with a solution comprising at least one Group VIB metal source and/or at least one Group VIII metal source, followed by a step of impregnating the carrier with a solution comprising a sulfur containing organic additive. 
     
     
       8. The method of  claim 1 ,  2  or  5  wherein the titanium source is selected from the group consisting of titanyl sulfate, titanium sulfate, titanium alkoxide or Titanium(IV)bis(ammonium lactato)dihydroxide.